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Publication numberUS6194595 B1
Publication typeGrant
Application numberUS 09/299,627
Publication dateFeb 27, 2001
Filing dateApr 27, 1999
Priority dateApr 30, 1998
Fee statusLapsed
Also published asCA2270502A1, CN1172938C, CN1247867A, DE19819373A1, EP0955302A1, EP0955302B1
Publication number09299627, 299627, US 6194595 B1, US 6194595B1, US-B1-6194595, US6194595 B1, US6194595B1
InventorsRudolf Michel, Jörg Münzenberg
Original AssigneeDegussa-Hüls Aktiengesellschaft
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the preparation of mixtures of organosilicon oligosulfanes containing a high proportion of organosilicon disulfanes
US 6194595 B1
Abstract
A process for the preparation of mixtures of organosilicon disulfanes with a high disulfane content includes first reacting finely divided sodium and sulfur in an organic solvent, and then reacting the resulting Na2Sx, product further with a halogenoalkylalkoxysilane to give the desired product.
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Claims(8)
We claim:
1. A process for preparing a mixture of organosilicon oligosulfanes containing a high proportion of disulfanes of the general formula:
Z-Alk-Sx-Alk-Z  (I)
wherein each Z, which may be the same or different, represents the group:
wherein each R1, which may be the same or different, is a member selected from the group consisting of a linear or branched alkyl group having 1-6 carbon atoms, a cycloalkyl radical having 5-8 carbon atoms, a benzyl radical, and a phenyl radical, wherein said phenyl radical may be optionally substituted by methyl, ethyl or chlorine; and
wherein each R2, which may be the same or different, is a member selected from the group consisting of an alkoxy group with a linear or branched carbon chain having 1-6 carbon atoms, a cycloalkoxy group having 5-8 carbon atoms, a phenoxy group, and a benzyloxy group,
wherein each Alk, which may be the same or different, is a divalent, saturated linear or branched hydrocarbon radical having 1-10 carbon atoms, or the group
wherein each n, which may be the same or different, is from 1 to 4, and wherein x is from 1.5 to 3.0,
the process comprising:
reacting a suspension of finely divided sodium with sulfur, in amounts corresponding to a stoichiometry of an Na2Sx product to be prepared, in a first inert organic solvent, at temperatures above 98° C., under an inert gas, to thereby form the Na2Sx product;
filtering the Na2Sx product;
dissolving or suspending the Na2Sx product, partially or completely, in a second inert organic solvent;
reacting the Na2Sx in the second organic solvent with a compound of general formula (II):
Z-Alk-Hal  (II),
 wherein Z and Alk are as defined above, and wherein Hal is a chlorine or bromine atom, to thereby fonn an organosulfane mixture; and
isolating the organosulfane mixture.
2. The process according to claim 1, wherein the first inert organic solvent has a boiling point greater than 98° C., and at least partially dissolves sulfur.
3. The process according to claim 1, wherein the reacting of finely divided sodium with sulfur is carried out under a pressure greater than atmospheric pressure.
4. The process according to claim 2, wherein the reacting of finely divided sodium with sulfur is carried out under a pressure greater than atmospheric pressure.
5. The process according to claim 1, wherein the sodium and the sulfur to be reacted in suspension are introduced simultaneously into a cylindrical reactor at spatially separated points.
6. The process according to claim 2, wherein the sodium and the sulfur to be reacted in suspension are introduced simultaneously into a cylindrical reactor at spatially separated points.
7. The process according to claim 3, wherein the sodium and the sulfur to be reacted in suspension are introduced simultaneously into a cylindrical reactor at spatially separated points.
8. The process according to claim 4, wherein the sodium and the sulfur to be reacted in suspension are introduced simultaneously into a cylindrical reactor at spatially separated points.
Description
FIELD OF THE INVENTION

The invention relates to the preparation of organosilicon oligosulfane mixtures containing a high proportion of disulfanes.

BACKGROUND OF THE INVENTION

Processes for the preparation of oligosulfanes have long been known. Various known systems are described below.

DE-PS 2141159 (U.S. Pat. No. 3,842,111) describes a process for the preparation of bis-(alkoxysilylalkyl) oligosulfanes from the corresponding halogen alkylalkoxysilane and alkali metal oligosulfides, preferably in alcoholic solution. However, only mixtures of sulfanes with different chain lengths are produced. These patent documents are entirely incorporated herein by reference.

In a process described in DE-PS 2712866 (U.S. Pat. No. 4,129,585), an alkali metal alcoholate is reacted with a halogen alkylalkoxysilane, metal or ammonium hydrogen sulfide, and sulfur in the presence of an organic solvent. However, the preparation of the alkali metal alcoholate solution is very time-consuming, which makes industrial-scale use of this process problematic. These patent documents also are entirely incorporated herein by reference.

U.S. Pat. No. 5,466,848 discloses a process in which hydrogen sulfide is reacted with an alkoxide, and the reaction product is treated with elemental sulfur, and then with a halogen alkylalkoxysilane, to give the desired organosilicon polysulfane. Likewise, the process according to U.S. Pat. No. 5,489,701 involves working with alkoxides and hydrogen sulfide, a compound which is known to be very unpleasant to handle. JP-OS 7-228588 describes the reaction of anhydrous sodium sulfide and sulfur with halogen alkoxysilanes. This procedure gives a mixture of polysulfanes, as experiments have shown. These three patent documents also are entirely incorporated herein by reference.

Organosilicon polysulfanes, and especially bis(triethoxysilylpropyl)tetrasulfane, are used in combination with highly active silicic acid fillers in the manufacture of vulcanized rubber articles, especially tires.

The advantageous use of high purity disulfanes in terms of both the processing of the material, and of the resulting properties of the vulcanizates, is set out in EP-A 0 732 362 (U.S. Pat. No. 5,580,919) and by Panzer (L. Panzer, American Chem. Soc., Rubber Div. Meeting, 1997). These documents also are entirely incorporated herein by reference.

The Na2Sx required for disulfane preparation can be obtained by reacting sulfur and sodium in molten form, as described in DE-PS 38 03 243, which document is entirely incorporated herein by reference. It should be noted, however, that the melting point of the polysulfide is inversely proportional to its sulfur content. Thus, for example, the Na2S2 required to produce oligosulfane mixtures of high disulfane content has a melting point of 474° C. The only suitable reactor material for such a high temperature is graphite. The difficulties of obtaining reactor components in the necessary dimensions makes industrial application of this process impractical.

DESCRIPTION OF THE INVENTION

The object of the invention is to provide a process for the preparation of organosilicon disulfanes, which process uses a Na2Sx product prepared from elemental sodium and sulfur.

The invention provides a process for the preparation of organosilicon disulfanes of the general formula:

Z-Alk-Sx-Alk-Z  (1)

in which the Z components, which may be the same or different, represent the groupings:

in which each R1 in the formula, which may be the same as or different from the other R1 groups in the formula, is a linear or branched alkyl group having 1-6 carbon atoms, a cycloalkyl radical having 5-8 carbon atoms, a benzyl radical, or a phenyl radical optionally substituted by methyl, ethyl or chlorine, and wherein each R2 in the formula, which may be the same as or different from the other R2 groups in the fonnula, is an alkoxy group with a linear or branched carbon chain having 1-6 carbon atoms, a cycloalkoxy group having 5-8 carbon atoms, a phenoxy group, or a benzyloxy group, and

wherein Alk, each of which may be the same or different, is preferably a divalent, saturated linear or branched hydrocarbon radical having 1-10 carbon atoms, preferably methylene, as well as preferably ethylene, i-propylene, n-propylene, i-butylene or n-butylene, also n-pentylene, 2-methylbutylene, 3-methylbutylcne, n-pentylene, 1,3-dimethylpropylene and 2,3-dimethylpropylene, with n-propylene being particularly suitable, or the group

where n=1-4 (wherein each “n” may be the same or different), and wherein x=1.5 to 3.0.

The process includes a two-step reaction, in which:

1. suspensions of finely divided sodium are reacted with sulfur in amounts corresponding to the stoichiometry of the Na2Sx product to be produced (e.g., in approximately equimolar amounts for a disulfane product), in an inert organic solvent at temperatures above 98° C., and optionally washed and dried (to thereby form an Na2Sx product), and then

2. the Na2Sx product is partially or completely dissolved or suspended in an inert organic solvent, and this solution or suspension is reacted with an organosilicon compound of general formula (II):

Z-Alk-Hal  (II),

in which Z and Alk are as defined above and Hal is a chlorine or bromine atom. After this second reaction step, the desired oligosulfane mixture is isolated.

The proportion of disulfane is preferably 55 to 100 wt. %, and more preferably 55 to 75 wt. %.

The desired oligosulfane mixture may be isolated by any suitable procedure known in the art. For example, the precipitate of inorganic halide can be filtered off, and the solvent can be separated off by distillation or evaporation.

Suitable solvents for step 1 are the known aliphatic hydrocarbons with a carbon chain length of 7 to 12 carbon atoms, and especially 7 to 9 carbon atoms; aromatic hydrocarbons, such as toluene, xylene, ethylbenzene, mesitylene, naphthalene, and tetrahydronaphthalene; or high-boiling ethers, such as ethylene glycol diethyl ether, dibutyl ether, dipentyl ether, and anisole; or mixtures of these solvents. Common features of these solvents are that they preferably boil above 98° C. and at least partially dissolve sulfur.

Advantageously, the sodium is present in the form of small molten beads, so that no passivation of the surfaces occurs due to the reactions with sulfur.

It is possible, however, to use solvents with a lower boiling point if the reaction is carried out under a pressure elevated above atmospheric pressure. The latter variant (i.e., using elevated pressure) is naturally also applicable to use with higher-boiling compounds.

In a preferred embodiment, a suspension of finely divided sodium, in the same solvent as the suspension of sulfur, is added dropwise to the latter.

However, it is also possible to meter finely divided sulfur into a sodium dispersion. In any case, it must be noted that the reaction of these elements is strongly exothermic, although this reaction is readily controllable by those skilled in the art.

The reaction takes place at temperatures of greater than 98° C. to 250° C., and preferably at 100 to 150° C.

Another advantageous embodiment of the invention includes a process wherein sodium and sulfur in the form of suspensions in the same solvents are introduced simultaneously into a cylindrical reactor at spatially separated points, the sulfur being added outside the sodium/sulfur reaction zone and in the agitated flow, as far as possible upstream of the sodium addition point.

The starting substances of formula (II) for the second step of the process can be prepared by the skilled artisan through known processes and are generally available.

Organic solvents which can be used for the second reaction step of the process according to the invention are basically any polar substances in which the Na2Sx is at least partially soluble and which do not react with the organosilicon compound of formula (II). A linear or branched alcohol having 1-5 carbon atoms, e.g., methyl, ethyl, propyl, butyl or pentyl alcohol, is preferably used as this organic solvent. Cycloalkyl alcohols having 5 to 8 carbon atoms, phenol, or benzyl alcohol are also suitable.

It is advantageous to use the alcohol corresponding to the particular R2 group, for example, to avoid a transesterification. It is also advantageous, if appropriate, to use a mixture of these alcohols, for example, if R2 in a compound of formula (I) has different meanings.

The process according to the invention affords a very pure disulfane with an average sulfur chain length of 1.97 to 2.06, which, in respect of the disulfide content, is markedly superior to the products prepared according to the state of the art, without a further purification step.

The following examples are provided to more clearly describe specific embodiments of the invention. These examples should be construed as illustrating this invention, and not as limiting it.

EXAMPLE 1

In a 500 ml three-necked flask equipped with a reflux condenser, a stirred dropping funnel, and a stirrer, a suspension of 11.5 g (0.50 mol) of finely divided sodium in 100 ml of xylene was added dropwise at 140° C., with stirring, to a suspension of 16.8 g (0.52 mol) of sulfur in 100 ml of xylene. The reaction is strongly exothermic. When the exothermicity has subsided after the drop-wise addition, a greyish-yellow heterogeneous reaction mixture is obtained which is kept at 140° C. for a further 30 minutes. After cooling, the solid is filtered off and rinsed with a low-boiling petroleum ether. The filter cake is dried by having dry nitrogen blown through it.

The dried filter cake is placed in 220 ml of ethanol in a 500 ml three-necked flask equipped with a stirrer, a dropping funnel, and a reflux condenser. A yellow solution is formed which warms to 65° C. After heating to 80° C., 114.4 g (0.48 mol) of 3-chloropropyltri-ethoxysilane are added dropwise to the boiling solution. When the dropwise addition has ended, the reaction mixture is left to react for a further 2.5 hours, with stirring, and cooled, and the insoluble material filtered off. The filter cake is rinsed four times with 50 ml of ethanol, and the filtrates are combined with the bulk solution. After evaporation under vacuum at 120° C. with a final vacuum of 40 mbar, 109.9 g of a brown liquid are obtained which, according to its 1H NMR spectrum, includes an oligosulfane mixture of the general fonnula [(EtO)3SiCH2CH2CH2]2Sx with an average sulfur chain length of 2.06. The yield is 92%, based on the amount of sodium used.

EXAMPLE 2

11.5 g (0.5 mol) of sodium is placed in 100 ml of xylene in a 250 ml three-necked flask equipped with a reflux condenser, a solid metering device, an Ultra-Turrax, and a stirrter. After heating to 110°C., the sodium is finely dispersed with the Ultra-Turrax. 16.0 g (0.5 mol) of sulfur is then added via the solid metering device, a violent reaction with fire occurring immediately on contact with the sodium suspension. While the sulfur is being metered in, the Ultra-Turrax is run 12 times for 1 minute in order to redisperse the sodium. When the metered addition has ended, the mixture was left to stand for a further 1 hour at 140-142° C., with stirring. After cooling, the yellow solid formed was filtered off and dried by having dry nitrogen blown through it.

The dried filter cake is placed in 220 ml of ethanol in a 500 ml three-necked flask equipped with a stirrer, a dropping funnel, and a reflux condenser. A yellow solution is formed which warms to 40° C. After heating to 80° C., 120.4 g (0.50 mol) of 33-chloropropyltri-ethoxysilane is added drop-wise to the boiling solution. When the drop-wise addition has ended, the reaction mixture is left to rcact for a further 2 hours, with stirring, and cooled, and the insoluble material is filtered off. The filter cake is rinsed four times with 50 ml of ethanol and the filtrates are combined with the bulk solution. After evaporation under vacuum at 120° C. with a final vacuum of 40 mbar, 110.6 g of a brown liquid is obtained which, according to its 1H NMR spectrum, includes an oligosulfane mixture of the general formula [(EtO)3SiCH2CH2CH2]2Sx with an average sulfur chain length of 1.97. The yield is 93%, based on the amount of sodium used.

Further modifications and variations of the foregoing will be apparent to those skilled in the art, and are intended to be encompassed by the claims appended hereto.

German priority application 198 19 373.4 is relied upon and incorporated herein by reference in its entirety.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3842111Aug 1, 1972Oct 15, 1974DegussaSulfur containing organosilicon compounds
US3978103May 6, 1974Aug 31, 1976Deutsche Gold- Und Silber-Scheideanstalt Vormals RoesslerBonding agents, vulcanization
US4129585Mar 7, 1978Dec 12, 1978Deutsche Gold- Und Silber-Scheideanstalt Vormals RoesslerNo formation of hydrogen sulfide
US4507490 *Mar 26, 1984Mar 26, 1985Degussa AktiengesellschaftSulfiding a haloalkylorganosilane
US4595740 *Jul 13, 1983Jun 17, 1986Degussa AktiengesellschaftWater insoluble, organic solvent insoluble
US5440064 *Dec 23, 1994Aug 8, 1995The Goodyear Tire & Rubber CompanyProcess for the preparation of organosilicon disulfide compounds
US5466848Sep 28, 1994Nov 14, 1995Osi Specialties, Inc.Process for the preparation of silane polysulfides
US5468893 *Dec 19, 1994Nov 21, 1995The Goodyear Tire & Rubber CompanyPreparation of sulfur-containing organosilicon compounds
US5489701Feb 2, 1995Feb 6, 1996Osi Specialties, Inc.Process for the preparation of silane polysulfides
US5580919Mar 14, 1995Dec 3, 1996The Goodyear Tire & Rubber CompanySilica reinforced rubber composition and use in tires
US5583245 *Mar 6, 1996Dec 10, 1996The Goodyear Tire & Rubber CompanyReacting haloalkylsilane compound with ammonium or alkali metal hydrosulfide and sulfur in presence of phase transfer catalyst and aqueous phase
US5663395 *Nov 5, 1996Sep 2, 1997Degussa AktiengesellschaftDesulfurization, tires
US5859275 *Dec 5, 1997Jan 12, 1999Degussa AktiengesellschaftSulfiding
US5892085 *Aug 10, 1998Apr 6, 1999Degussa AktiengesellschaftReaction of sulfur, alkali sulfide, halogen alkylalkoxysilane in a two stage process
EP0326914A1Jan 25, 1989Aug 9, 1989Degussa AktiengesellschaftProcess for preparing sodium polysulphides from elementary sodium and sulphur
JPH07228588A Title not available
Non-Patent Citations
Reference
1Database WPI on Questel, Woche 9543, London: Derwent Publications Ltd., AN 95-332519 & JP 07228588.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6274755 *Jun 30, 2000Aug 14, 2001Degussa-Huls AgProcess for the production of polysulfide silane compounds
US6380413 *May 10, 2001Apr 30, 2002Degussa AgProcess for the preparation of yellow bis (3-[triethoxysilyl]propyl) tetrasulfane
US6384256 *Jun 29, 2001May 7, 2002Dow Corning CorporationReacting alkali metal hydroxide, sulfide compound, elemental sulfur and alkylalkoxy silane; phase transfer catalysis; minimizing hydrogen sulfide emission
US6423859 *Jul 13, 2001Jul 23, 2002Degussa AgReacting ionic sulfide and organsilylalkyl-halide; promoting adhesion/reinforcement in rubber mixtures comprising oxidic fillers
US6448426 *Jun 29, 2001Sep 10, 2002Dow Corning CorporationProcess for the preparation of sulfur-containing organosilicon compounds
US6465672 *Mar 1, 2001Oct 15, 2002Degussa AgProcess for the production of organosilylalkyl polysulfanes
US7687558Dec 28, 2006Mar 30, 2010Momentive Performance Materials Inc.Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions
US7696269Dec 28, 2006Apr 13, 2010Momentive Performance Materials Inc.With a vulcanizable natural rubber, synthetic polyisoprene rubbers, polyisobutylene rubbers, polybutadiene rubbers, or styrene-butadiene rubbers; (2-triethoxysilylethyl)-bis-(7-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; tires; reduced rolling resistance; improved fuel economy
US7737202Dec 28, 2006Jun 15, 2010Momentive Performance Materials Inc.bis-(3-triethoxysilylpropyl) disulfide, bis-(3-triethoxysilylpropyl)tetrasulfide and 1,2,4-tris(6-triethoxysilyl-3,4-dithiaheptyl)cyclohexanel; vulcanizable rubber such as natural rubbers, synthetic polyisoprene, polybutadiene, random styrene-butadiene copolymer; silica as reactive filler
US7781606Dec 28, 2006Aug 24, 2010Momentive Performance Materials Inc.Blocked mercaptosilane coupling agents, process for making and uses in rubber
US7960460Dec 28, 2006Jun 14, 2011Momentive Performance Materials, Inc.Free-flowing filler composition and rubber composition containing same
US7968633Dec 28, 2006Jun 28, 2011Continental AgA vulcanizable natural rubber, synthetic polyisoprene rubbers, polyisobutylene rubbers, polybutadiene rubbers, or styrene-butadiene rubbers and a silated polysulfide; (2-triethoxysilylethyl)-bis-(7-triethoxysilyl-3,4,5,6-tetrathianonyl)cyclohexane; reduced rolling resistance; improved fuel economy
US7968634Dec 28, 2006Jun 28, 2011Continental Agbis-(3-triethoxysilylpropyl) disulfide, bis-(3-triethoxysilylpropyl)tetrasulfide and 1,2,4-tris(6-triethoxysilyl-3,4-dithiaheptyl)cyclohexanel; vulcanizable rubber such as natural rubbers, synthetic polyisoprene, polyisobutylene, polybutadiene, and random styrene-butadiene copolymer; an active filler
US7968635Dec 28, 2006Jun 28, 2011Continental AgTire compositions and components containing free-flowing filler compositions
US7968636Dec 28, 2006Jun 28, 2011Continental AgTire compositions and components containing silated cyclic core polysulfides
US8067491Feb 16, 2010Nov 29, 2011Momentive Performance Materials Inc.Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions
US8188174Feb 9, 2010May 29, 2012Momentive Performance Materials Inc.Silated core polysulfides, their preparation and use in filled elastomer compositions
US8383850Jun 22, 2010Feb 26, 2013Momentive Performance Materials Inc.Blocked mercaptosilane coupling agents, process for making and uses in rubber
US8501849Apr 27, 2012Aug 6, 2013Momentive Performance Materials Inc.Silated core polysulfides, their preparation and use in filled elastomer compositions
US8592506Dec 28, 2006Nov 26, 2013Continental AgTire compositions and components containing blocked mercaptosilane coupling agent
US8669389Jan 18, 2013Mar 11, 2014Momentive Performance Materials Inc.Blocked mercaptosilane coupling agents, process for making the uses in rubber
Classifications
U.S. Classification556/427
International ClassificationC07F7/18, C07F7/08
Cooperative ClassificationC07F7/1892
European ClassificationC07F7/18C9G
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